4-Bromo-N-(diisopropoxyphosphor­yl)benzamide

Christoph E Strasser; Xia Sheng; Damir A Safin; Helgard G Raubenheimer; Robert C Luckay

doi:10.1107/S1600536809044523

. 2009 Oct 31;65(Pt 11):o2926. doi: 10.1107/S1600536809044523

4-Bromo-N-(diisopropoxyphosphoryl)benzamide

Christoph E Strasser ^a, Xia Sheng ^a, Damir A Safin ^b, Helgard G Raubenheimer ^a, Robert C Luckay ^a,^*

PMCID: PMC2971034 PMID: 21578503

Abstract

In the title compound, C₁₃H₁₉BrNO₄P, the crystal structure is stabilized by intermolecular N—H⋯O hydrogen bonds between the phosphoryl O atom and the amide N atom which link the molecules into centrosymmetric dimers. These dimers are further packed into stacks along the c axis by intermolecular C—H⋯O and C—H⋯π interactions.

Related literature

For the synthesis, see: Safin, Sokolov, Baranov et al. (2008 ▶). For related structures, see: Chekhlov (1990 ▶); Safin et al. (2009 ▶); Safin, Sokolov, Nöth et al. (2008 ▶); Solov’ev et al. (1990 ▶). For the chemistry of phosphine derivatives of urea and thiourea, see: Birdsall et al. (1999 ▶). For the use of bidentate organophosphorus ligand systems, see: Crespo et al. (2004 ▶); Safin et al. (2006 ▶) and for the transport and extraction of metal ions, see: Luckay et al. (2009a ▶,b ▶).

Experimental

Crystal data

C₁₃H₁₉BrNO₄P
M _r = 364.17
Monoclinic,
a = 8.611 (1) Å
b = 19.786 (3) Å
c = 9.849 (1) Å
β = 95.357 (2)°
V = 1670.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 2.57 mm⁻¹
T = 100 K
0.32 × 0.07 × 0.05 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.494, T _max = 0.893
9035 measured reflections
3405 independent reflections
2604 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.120
S = 1.05
3405 reflections
185 parameters
H-atom parameters constrained
Δρ_max = 1.29 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶; Atwood & Barbour, 2003 ▶); software used to prepare material for publication: X-SEED.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809044523/lx2117sup1.cif

e-65-o2926-sup1.cif^{(18.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809044523/lx2117Isup2.hkl

e-65-o2926-Isup2.hkl^{(167KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.88	1.96	2.819 (3)	166
C3—H3⋯O4ⁱⁱ	0.95	2.29	3.213 (4)	163
C6—H6⋯O1ⁱ	0.95	2.48	3.241 (3)	137
C16—H16C⋯Cgⁱⁱⁱ	0.98	2.63	3.608 (4)	173

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg is the centroid of the C1–C6 benzene ring.

Acknowledgments

We would like to thank the National Research Foundation (NRF) of South Africa for financial support.

supplementary crystallographic information

Comment

The chemistry of phosphine derivatives of urea and thiourea was first studied during the 1960 s (Birdsall et al., 1999). Subsequently, related bidentate organophosphorus ligand systems were developed to form R¹C(X)NHPR₂ and their derivatives (Safin et al., 2006). Different R¹C(X)NHP(Y)R²R³ (R¹ = RNH or NZ₂ with Z = H, alkyl or aryl; R², R³ = alkyl, aryl, alkoxy or aryloxy; X, Y = O, S, Se) have been reported (Crespo et al., 2004). These types of ligands have recently been used successfully as ionophores for the transport and extraction of a number of metal ions (Luckay et al., 2009a, 2009b). Here we report the crystal structure of the title compound (I) (Fig. 1).

The crystal structure is stabilized by intermolecular N—H···O hydrogen bonds between the phosphoryl O atom and the amide N atom which link the molecules into centrosymmetric dimers (Table 1 and Fig. 2). These dimers are further packed into stacks along the c axis by intermolecular C—H···O and C—H···π interactions; the first between the benzene H atom and the oxygen of the C═O unit, with a C3—H3···O4ⁱⁱ, the second between the benzene H atom and the oxygen of the P═O unit, with a C6—H6···O1ⁱ, the third between the methyl H atom of the isopropyl group and the benzene ring, with a C16—H16C···Cgⁱⁱⁱ (Cg is the centroid of the C1–C6 benzene ring), respectively (Table 1 and Fig. 2).

Experimental

4-bromo-N-(diisopropoxyphosphoryl)benzthioamide was prepared according to the procedure of Safin et al. (2009). This ligand and one equivalent of copper(I) iodide was dissolved in acetone and heated to 50 °C for 2 hours. The colourless powder obtained was dissolved in a minimal quantity of THF and allowed to slowly evaporate. After 6 days, colourless needles were deposited. The hydrolysis of the thione group group was most likely caused by the presence of moisture in the solvents as well as the presence of the Cu⁺ ion.